Sensitizing dyes containing a 4-aryl-5-aryloxy- or 5-arylthiothiazole nucleus



e 4:34 m sENsI'rIzuvo 'YES coN'rAmu G XmARYL-stg r gxY- R5-ARYLTHIOTHIAZOLE NU- Edward B. Knott, Harrow, England, assignor toEastman United s affisfyPatent O Kodak Company, Rochester, N. Y., acorporation. of

New Jersey No Drawing. Application March 28, 1952, Serial No. 279,209

13 Claims. (Cl. 260-4401) This invention relates to new polymethine dyeswhich areuuseful in optically sensitizing photographic silver halideemulsions and to methods for. preparing such dyes.

wherein R represents an alkyl group,ysuch"as" methyl,

ethyl, p-hydroxyethyl, etc., R1 and R: each represents an aryl group,such as phenyl, 0-, m and p-chlorophenyl,

and ,B-naphthyl, etc, X represents an oxygen or sulfur;

atom, L represents a methine group (e g. =CH--,

1 of Lande (J. C. S. 1903, vol. 83, 417).

acylated compounds (i. e. where R3 is acyl) are preferred for dyecondensations. The condensationof the compounds of Formula II with thoseof Formula III can be accelerated by heat and can be performed in thepresence of an inert diluent, if desired (e. g. lower aliphatic alcohol,such as .ethanol, n-butanol, etc.) acetone, pyridine, etc.

The compounds of Formula II above canaadvantageously be preparedaccording to the method described in U. S. Patent 2,487,882, issuedNovember 15, 1949. Such amethod comprises reacting a quaternary saltselected rorn those represented bythe following general formula: IV.

RrX-C R C-CH| e t r wherein R, R1, R2, X, and X1 have the values givenabove with a compound selected from those represented by the followinggeneral formula:

wherein R4 has the values given above and R5 represents an alkylgroup,,such as methyl, ethyl, etc. Compounds represented by Formula Vcanbe'prepared by the method (See U. 5. Patent 2,487,882.) The acylatedcompounds of Formula II can be prepared by heating the compounds whereinR s represents a hydrogen atom in the presence of a carboxylicanhydride. i i

: The compounds represented by Formula IV above can advantageously beprepared by condensing a halogenatedketonyl ether or halogenated ketonylthioether selected from those represented by the following generalformula:

VI. 0 X

.. by FormulaVI can be prepared by halogenating a ketone non-metallicatoms necessary to"complete a heterocyclic nucleus containing five atomsin the heterocyclic ring, three of saidatoms being carbon atoms, oneofsaid atoms being anitrogen atom and one ofsaid atoms being selectedfrom thegroup consisting of an oxygen atom and a sulfur atom. r

The inerocarbocyanine dyes represented by Formula I above canadvantageously be prepared by condensing a compound selected from theserepresented by the following general formula: e

with a ketomethylene compound selected from fthose represented by thefollowing general formula: III. I /Q\ H,o---o=o wherein R, R1, R2, X,and Q have-the values given above,

R3 represents a hydrogen atom or an acyl group (e. g. acetyl,propionyl,-benzoyl, etc.), R4 represents an aryl group (e. g. phenyl,0-, m-, and p-tolyl, etc.), and X1 f represents an acidradical, such aschloride, bromide, iodide, benzenesulfonate, p-toluenesulfonate,methylsulfate, ethylsulfate, perchlorate, thiocyanate, etc. The

R1--EJA7H'XR: wherein R1, Rn, and X have the values given above and X2represents a halogen atom (e. g. chlorine, bromine, etc.),withthioacetamide. The compounds represented selected from those representedby the following general wherein R1, R2, and X have the values givenabove. The

halogenations can advantageously be carried out inthe presence of aninert solvent,.such..as carbon bisulfide, chloroform, carbontetrachloride, etc. A number of w-aryloxyacetophenones of Formula VIIhave been described by Moehlau, Berichtef vol.; 15 (1882), pg. 2497. Anumber of w-arylthioacetophenones of Formula VII have been described byDelisle, Berichte," vol. 22 (1889), 309. The conventional Williamsonether synthesis was employed in my invention to produce the ketonylethers and ketonyl thioether.

w-Aryloxyacetophen0nes.+-These were prepared as follows:

Potassium hydroxide (1 mol.) was dissolved in industrialmethanol (750cc.) by heating on a steam bath.

.The requiredphenol (1 mol.) was then added and the solution cooledto 30C. The addition of the required phen- (or naphth-) acylbromide (1 mol.)with eflicient 45 C.) and separationof potassium bromide. On standingfor one hour followed by chilling, the required agitation caused atemperature increase (to about 40- w-aryloxyacetophenone then separated.It was collected,

washed with a little ice-cold ethanol and water until all solublebromide was removed. Alternatively it was re Patented Apr. 24, 1956 a A3 I 3, J H n E: czystalli zedrffrom-ethanol? The'ifollowin'g" table'gives the The quaternary salts ofForinula IV "wherein X"i'epr'properties of representatwe w-aryloxyacetophenones obsents an oxygenatom were prepared by heating the abovev tamed 1n the above manner.thiazole bases (Table 11) together with an alkyl salt.

TABLE I w-Arylthioacetophenones, w-bromo w arylthioaceto- 5 ph enones,and 4 aryl 5 arylthio-Z-methylthiazales.-- u These intermediates were'prepa red in the same manner as the. corresponding aryloxy. comppunds..described Ri Big fig Appearance .C'tHsi CsHJ-. 77 72 white needles.pCH50.'-.CqH4E-.- 0035 72' 65} l small plates.

Ca r' p-.(t- OuH GlsHr-r- 50- 76' 76.'-5 flatneedles. .D- a'- J u' l- Ip-(faHfilCsfli- 90 102 I waxy plates .CtHta p-OtHilOHI- 04:: flakes.

D me-Odie? D-.C1Qe .r-.- 52-- 132-133 glossy needles. a )'i 0 T p-Ci sO-QHE- 70 103 threads.

p-BrCgH;- p-Br--CH 63 133-135 laths.

w-Bromo w aryl oxyactopher'zon'esP-The w-aryloxyabove; The-followingzeitample's willi' se'rve to intimates- 1 acetophenones (1 mol.)obtained above were dissolved thisi general proeedureiz. in carbonbisulfide or chloroform (1 liter) and were i z w i treated at 5 c. (orhigher, e. g. 50-60 C.,if reaction Example4W-WPJOIYMwmmphmo'wwas-slower-)with'- a solutiono'fbromine-(l mol.) iirthe Pijtassiumi.hydf' jxidi' 4. ;:5 ggmdi 0N d-m..i a.

same selvent 5 The f m k t i as-is ldust'riai;methylated.spirit'i(400:ec.)=and =thioeresoltt9 either byevaporation of the-solvent by*-air or by'washgx d Tithei 'oli tibfl ingwith dilute aqueoushsodiumrcarbonate, then water, bromide:( 155 -at 30C.was added-'phenaeyl 'and the whole-weli a itated; Potassium and removingthe solvent onthe steam .bath under rebromide separated "and thetemperature rose '-to =60 -Ci duced'pre'ssure. The resultant solids oroils were un- After 30 minutes the' whole was-chilled-'arid the l 'whichstable and used'in' most cases'without purification; Folseparatedirapidly crystallized? Water" (400"-ce.-) was 10w fig,;arethe constantsof several brominated 'o s added anda-the 'crystals colleetedgwashedwitltwater'tlieh which werepurifi'edz with a little ethanol. Yield' l'SSgE (983%292- A sample" l...w-Bromo-w-phenoxyacetophenone; needles, M. P.72

fromlight petroleum-. Exam le B. -Brom0- -tol lthibacet' I enon 2.w-Bromo-p-methoxy-w-phenoxyacetophenone,. crysp w (up y 0P 1 e fromethanol formed short, glassy needles, M. P. 40 C.

V talline. balls,.M-..P'. 80-381 C..from-.-ligroin.. The crudew-p-tolylthioacetophenone (24.2 g.) was 3.- wfBromo-p-chloro-w-(p;chlor0phenoxy)aacetophenone; dissolved in chloroform (100 cc.) andcooled to 10 C. plates, P;- 158? C. from ethanol. A solution of bromine(5.15 cc.) inzchloroform (2.5 cc.) 4.; w,p;dibromo 1- w (p,-bromophenoxy) acetophenone, was. dripped into. theabove .over... 15minutes Bromine. needles, M. P. 157 C. from ethanol. absorptionMasrapidCH V I. 40 Thetclilorof orm was removed.in,an airstreanttmgive1 4-aryl 5aryloxy 2 methylthmzoles These were pre 30 g yl qw y fl P: C. A sampleframpared as follows. th v The bromoketones"('1-rnol.)'obtainedabovewere-dis l x' 3. 1 solved'or suspendedin ethanol (500ecz) 'and"thi0acet-" xam eczliyzztmefhyle4zpli'gnybs-ptolylthibtfiiazble some cases there was somespontaneous crystallizgtidn untilreactionzsetxiri asshoiwnrbwa riseinttell)pel'aturefitov of the hydrobromide salt of the'rfree thiazole,and in 6O.='C.' Thetwholecwasvrefiuxedfor 1 hour,; chilled and-z. allcases anhydrous ether-(2;.liters) was added to throwdry-:ethervUOOaeCLz) added... The;required.hydrobronude and if sticky,-was' slurr'ie'd withacetonet collect'ed and tai on a g the fi ra hhrdros f washed with acetone.- Thebase-wasobtained by 'disega'sa'The'scombmedr saltaavere washed:with.aeetone,.;dnssolving the saltinethanol; adding excessaqiieous sodiumsolvedumhot'isprnt :(250 ;.cc.)szalndithe.-.base :tlirown down' carbonateand=throwing 0ut"with wateri'ltwas -usually by 'addixig aqueouseiblr sodiumscarbonates:The;-.oil\wa's-.-; crystallized from ethanol. The r"oll"owing tablegives the- 5 extracted with ether, dried oversodium-sulphate.andttheeonstantsof several-of the thiazol'e Bases-thusobtained;- ether distilled. The residual oil wasdistilled at 200 C./ 6.mm. to give a pale yellow viscous-oil which slowly crys TABLEILtallized. From ligroin,.it- -formed slightly yellow glassy prisms, M. P.4142 C. R'r-O 'C' The following" examples will serve to illustrate morefully the manner whereby we prepare the intermediates represented byFormula II above wherein R3 represents a hydrogen atomre. v

Rt Ri gfigt; Appearance CaHj can. as 6a Hatd Aggregates; 'fi-cHg -'G5H4CaH' r E4v ..90x. vNeedles. p-CHr-.-OGHr- D"(t7OQHl1)GIH6 .34. -72.Plates. 00H; p-(C HQ'GBHL. 21- -s7-ss- Needles. -3,'4 oHt0)'=0tH,oamoyoam: 25 1 71-72:; :Soit Needles or-0,11; ot-06H; 3a.. 1001101,Rhomblel pair-06H. p-Brfotfli" I 59"" 76*77" Lathsn Example I .-2 ,3 5anilinovinyl 5 phenoxy 4 phenylthiazole ethiadide |Hi \N/ C1415 \I2-methyl-5-phenoxy-4-phenylthiazole (5.34 g.) andethyl-p-toluene-sulphonate (4 g.) were fused at 170 C. for 5 hours.Ethylisoformanilide (3 cc.) was added and the fusion continued for 1hour. Ethanol (15 cc.) was added to dissolve the red melt andan excessof saturated aqueous potassium iodide added. The addition of ether (25cc.) threw out a red oil which slowly crystallised. It was collected,washed with water and boiled up with ethanol (25 cc.). The reddishcrystals (3.3 g.) were pure enough for dye condensations. A sample fromethanol formed yellow needles M. P. 196 C.

Example 2.2 B anilino 5 phenoxy 4 phenylthiazolemetho-p-to'laenesulphonate Example 3.2 p anilinovinyl- 5 p(tctyl)phenoxy-4-phenylthiazole ethiodide t This intermediate formed asyellow needles, M. P. 176 C. from benzene-ethanol.

anilino 4 p anisyl phenoxy- Example 4.2 p s thiazole ethz'odide The base(1.5 g.) and ethylsulphate (0.7 cc.) were fused at 150 C. for 90minutes. Ethylisoformanilide (1 cc.) was added and the fusion at 150 C.continued for 30 minutes. It was convertedto the iodide and formedyellow needles, M. P. 196 C., from ethanol.

5.2 ,6 aniline 4 p T anisyl 5 phenoxy Example t thiazolemetho-p-toluenesulphonate This intermediate formed as 202 C., fromethanol.

Example 6.2 13 anilinovinyl 4 p anisyl 5 p (t-octyl)phenoxythiazolemetho-p-toluenesulphonate yellow needles, M. P.

This intermediate formed as 236 C., from ethanol.

Example 7.2 ,8 anilinovinyl 4 phenyl 5 p phenyl phenoxythiazolemethiodiae c lhis intermediate formed as yellow powder, M. P. 266 C.,after boiling up with acetone.

Example 8.-2 B anilinovinyl 5 p chlorophenoxy 4-p-chl0r0phenylthiazoleethiodia'e This intermediate formed as yellow-brown crystals, M. P. 247C., from ethanol.

Example 9.--2 fl anilinovinyl 4 (3,4dimethoxyphenyl)S-p-phenetoxythiazole ethiodiae This intermediate formedas soft, needles, M. P. 185 C., from ethanol.

glossy, yellow Example 10.2 3 anilinovinyl 5 p bromophenoxy 4-p-br0m01henylthiaz0le ethiodide This intermediate formed as brown crystalsQM. P.

193 C., from ethanol.

pale yellow needles, M. P. l

.iodide (9.5 g., 56. 5%). formed Example I 1.-2 -p -anilindvinyl-4-phenyl-5-ptolylthiothiazole ethiodide Ci \I2-methyl-4-phenyl-5-p 2 hours. Ethylisoformanilide (5 cc.) was added andfused a further hour at 150 C. Treated as Ex. 1, the a yellow powder, M,P.

- tolylthiothiazole (9 225 C.,- from ethanol. 1 r Example 12.2 RaniIiIIOvinyI 4 talylthiothiazole' 'methiodia'e This intermediate formedas glossy, yellow needles,

Example 14.--[3

thiazole] [3 ethyl 2 thio 5 dimethinemerocyanine t t 1 Product of Ex. 1(2.63 g.) and acetic anhydride (15 cc.) were refluxed for /2 hour andthe solvents removed under reduced pressure. 3-ethylrhodanine (0.8 g.),1

ethanol (10 cc.) and triethylamine (1 cc.) were added and the wholeheated on the steam bath for 10 minutes. An oil separated on coolingwhich crystallized overnight.

From ethanol it forms green needles M. P. 174 C. It

sensitizes a silver chlorobromide or iodobromide emulsion with a peak of610 mu.

Example 15.-[4 p anisyl 3 a methyl 5 phenoxy 2 thiazole] [2 ethylthio 4thiazol 5 f one] dimelhinemerocyanine f N-dithiocarbethoxyglycine -(2g.),.acetic anhydride (15 cc.) and ethyl orthoformate. (5 cc.) wereheated on the steam bath for 30 minutes and the solvents removed.

. ethanol (15 cc.). Triethylamine (1.5 cc.) was added and the wholeheated on the steam bath for 5 minutes. On

. cooling an oil separated. Methanol (10 cc.) was added and on boilingthe dye crystallized. Frombenzenet methanol it formed dark red needleswith green reflex, M. P. 168 C. Itsensitized a silver chlorobromidelwithapeakatSSOmu.

and ethylsulphate (4 cc.) were fused at C. for

phenyl v5 p ethyl 5'- phenoxy 4 phenyl 2 1 thiazolid -14 one] u Example26.- [3 Ethyl 4 p napltthyl-S-p-tolylthio-Z- thiazole][3-ethyl-2-thi0-5-thiaz0lid-4-ane] dimethinemerocyanine This dye wasobtained as garnet needles from benzenemethanol, M. P. 198 C., withmaxima at 630 mu (AgClBr) and 610 mu (AgIBr).

Cyanine (monomethine) and carbocyanine (trimethine) dyes can also beobtained according to my invention. Such dyes can advantageously beobtained by condensing a quaternary salt selected from those representedby Formula IV with a compound selected from those repre sented by thefollowing general formula:

wherein R3 represents an alkyl group, such as methyl, ethyl, n-propyl,fl-hydroxyethyl, fi-ethoxyethyl, etc., X3

represents an acid radical, such as chloride, bromide,

iodide, methylsulfate, ethylsulfate, benzenesulfonate,ptoluenesulfonate, perchlorate, etc., It represents a positive integerof from 1 to 2, Y represents an electro-negative group, such aschloride, bromide, alkylthio (e. g., methylthio, ethylthio, etc.),arylthio (e. g., phenylthio, ptolylthio, etc.), a ,B-arylarninovinylgroup (e. g., {3- acetanilidovinyl, etc.), etc, metallic atoms necessaryto complete a heterocyclic nucleus containing from 5 to 6 atoms in theheterocyclic ring, such as those of the thiazole series (e. g. thiazole,

oxy-a-naphthothiazole, etc.), those of the thionaphthenm.

7', 6, 4, S-thiazole series (e. g. 4-methoxy-thionaphand Z representsthe nonindolenine, etc.),

pyridine, 3-methylpyridine, 4-rnethylpyridine, 5-methyldroxyhenzoxazole, 6-hydroxybenzoxazole, etc.), those of (e. g.a-naphthoxazole, B-naph the naphthoxazole series thoxazole, etc.), thoseof the selenazole series (eg. 4- methylselenazole, 4-phenylselenazole,etc.), those of the benzoselenaz ole series (e. g. benzoselenazole,5-chlorobenzoselenazole, S-methoxybenzoselenazole,S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), those of thenaphthoselenazole series (e. g. u'naphthoselenazole,p-naphthoselenazole, etc.),those of the thiazoline sen'es (e. g.thiazoline, 4-methylthiazoline, etc.), those of the 2- quinoline series(e. g. quinoline, 3-methylquinoline, 5- methylquinoline,7-methylquinoline, S-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, G-ethoxyquinoline,6-hydroxyquinoline, 8-hydroxyquinoline, etc.), those of the 4-quinolineseries (e. g. quinoline, 6-methoxyquinoline, 7-methylquinoline, 8methylquinoline, etc.), those of the l-isoquinoline series (e. g.isoquinoline, 3,4-dihydroisoquinoline, etc.), those of the3-isoquinoline series (e. g. isoquinoline, etc.), those of the3,3-dialkylindolenine series indolenine, 3,3,5 trimethylindolenine,3,3,7 trimethylthose of the 2-pyridine series (e. g.

pyridine, 6-methylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine,3,6-dimethylpyridine, 4,5-dimethylpyridine, 4,6-dirnethylpyridine,4-chloropyridine, S-chloropyridine, 6-chloropyridine, 3-hydroxypyridine,4-hydroxypyridine, S-hydroxypyridine, 6-hydroxypyridine,3-phenylpyridine, 4-phenylpyridine, fi-phenylpyridine, etc.), those ofthe 4-pyridine series (e. g. Z-methylpyridine, S-methylpyridine,2-chloropyridine, 3-chloropyridine, 2,3-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2-

hydroxypyridine, 3-hydroxypyridine, etc.), etc.

The following samples will serve to illustrate the manner whereby Iprepare the mentioned above.

Example 27.--[] methyl-Z-quinolinc] [-ezhyl 5phenoxy-4-phenyl-2-thiazole] methinecyanirre iodide2-methyl-5-phenoxy-4-phenylthiazole (0.5 g) and di ethylsulphate (0.3g.) were fused at 150 C. for 1 hour. Z-methylthioquinolinemetho-p-toluenesulphonate (0.62 g.), ethanol (10 cc.) and triethylamino(0.3 cc.) were added and refluxed for 15 minutes on the steam bath. Asaturated solution of potassium iodide (1 cc.) was added and on cooling,the dye crystallized. From ethanol it formed orange threads, M. P. 258C. It sensitized a silver chlorobromide emulsion with a peak at 540 mu.

Example 28.Bis-(4-p-anisyl 3 methyl 5 phenoxy-Z- theno 7', 6', 4,S-thiazole, etc.), those of the oxazole series (e. g. 4-methyloxazole,S-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole,4,5-dimethyloxazole, S-phenyloxazole, etc.), those of the benzoxazoleseries (e. g. benzoxazole, S-chlorobenzoxazole, S-phenylbenzoxazole,S-methylbenzoxazole, 6-

methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole,S-methoxybenzoxazole, G-methoxybenzoie azole- S-ethoxybenzoxazole,6-chlorobenzoxazole, S-hy- OQHEO S C aw thiazole) trimethinecyam'neperchlorate Product of Ex. 5 (1.5 g.) and acetic anhydride (10 cc.)

were refluxed for 30 minutes and the solvent removed.

was added and the dye obtained as a tar on cooling. The

(e. g. 3,3-dimethyl-- cyanine and carbocyanine dyes 11 12 liquor wasdecanted, the tardi'ssolved in ethanol (15 cc.) such as ethanol,n-butanol, 1 ,4-dioxane, etc. can be used,, and amexcessof'saturatedaqueous sodium"-perch1orate if de'sii'ed.- i i added?The-dyeseparat'ed and formed 'a-bronzecrystal-Themerocarbocyanine=dyesof'the-types'rep 'esented by lihepowder,"M:P':140"Cl, fr'ommethanol: It sensitized Examples 14 to 26above can be heated togetherwitli an asilver chlorobromide emulsion:with a peak afi 5'40-mu 5 alkyl salt, such as methyl p-toluenesulfonate,ethyl p-toluandasil'ver iodobromid'e'witha peak at=6-10 mu;enesulfonate, methylsulfate, ethylsulfate, etc. to give dyes Example29.-Bis-(3-methyle4-phenyl'5-p talylthio-Z- thiazole)trimethinecyanineiodide This 'dye was obtained as flat; bronze'needles, M; P;ofwthe-typ'esrepresented by thefollbwing gcneral fo -m litia:

mide emulsion with a maximum at 540 muz Example 31.-Bis-(3rethyl-4-fl-naphthyl-S-p-tolylthio-Z- thiazole)trimethinecyanineiodide This dye was obtained as bronze prisms, M'. P. 194 (3., whereinR1, R2" and)! have thevalues-givemab'ove; R i' fnommethanollItsensitizeda silver chlorobromide emul-v and"R5'.each representsanallcyhgroup; such as methylfi si onswithia maximumat 630 mu. ethyl;etc;, and"'X4' represents an* acid'radical, sucl'i'= as p Thefollowingrstyryl dye was also obtained toluenesulfonate, ,ethylsulf'ate;methyls'ulfate; etc."

The: dyesof Formulas 1X and-X can-be condensedwviflfi Example32L-p-DimethylaminostyrylJ flamphthy[#5- 2-- W s one'of theketomethylenecompounds selected flOlIlffllOSG toiyhhl-z'thmzoleethoperchlumte rep 'esente'd by"Fo'1-mula*IIIiTtogive-complex-"(trinuclearyi CHRO-S. s merocyanine" dyes" represented" bythe 'fol'lowingg generalk' \C/ formulas:

g: C GH==C-H ON(OH 3)2H XI; R5 f =C--1 V Q\ -C -& he b-o 01115 610. RP CH-CH-- a. 2q-methyl-4-fl-naphthyl-5 -p tolylthiothiazole (O.7- g. N Sand diethylsulphate (O.3/cc.) were fused at 140C. for 90-\ k minutes.p-Dimethylaminobenzaldehyde (0.3 g.); etha- 1101 (10 cc.) and piperidine(0.1 cc.) were added and the an wholerefiuxed forBOminutes. Saturatedaqueous'isodium XIL, s1: penchlorate( 0t5cc.)gwasaddedandnthedyetcrystallizedc E-fon-standi g, Fromsm'ethanolitformed dulL echcxzystals,v I fl LL??? 1865 C. It sensitized asilverchlorobromide-emul--- 701 sionzwithapeak at 580 mu, t As; showngini the;above examples the condensations-can. I

can be condensed with a cyclammonium quaternary salt selected from thoserepresented by the following general wherein R, R1, R2, R3, R4, Rs, X,Xs, n, and Z have the values given: above. These condensations areaccelerated by heating in the presence of a .basic condensing" agent,such as triethylamine, tri-n-butylamine, triisoamylamine, N methylpiperidine, N ethylp iperidine, N,N dimethylaniline, N,N-diethylaniline,etc. lnertdiluents, such as ethanol, opropanol, propanoLfn-butanol,acetone 1,4

dioxane,etc., can be used.

The following examples will serve to illustrate the manner whereby Iprepare the novel complex merocyanine and cyanine dyes of my invention.

Example 33.-[3 ethyl 5 'phn'oxy 4 phenyl 2 thiazole] [2 (3 ethyl 4 keto2 thlo 5 thiazolidinylidene) 3 ethyl 5 rhiazolid 4oneldimethinemerocyanine can Product of Ex. 14 (0.75 g.) and methylptoluenesul' phonate (0.3 g.) were fused at 120 C. for 1 hour. 3-

ethylrhodanine (0.3 g.), ethanol (10 cc.) and trithylamine (0.3 cc.)were added and the whole heated for 10v minutes on the steam bath. Thedye separated, was filtered hot and washed with ethanol. From benzene itformed green crystals, M. P. 274 C. It sensitized a silver chlorobromideemulsion with a peak at 670 mu and a silver iodobromide emulsion with abroad maxi- [2-(3-ethyl-4-keto-2-thio rhiazolidinylidene) 3-ethyl-S-thiazolidi-one] dimethinemerocyanine V 65 t S This dye wasobtained as a green powder, M. P. 240

C., from pyridine-methanol with sensitizing maxima at 690 mu (AgClBr)and 680 mu (AgBrI).

6 mmo-c o=o--s n-0.x. fl o=cn-cn=e =s 10 N (5H:

H: "I -his dyewas obtained as green crystals; M. P. 286? C.,frompyridine with a sensitizing maximum "at 670 mu 5 (AgClBr). Example36. [4- p-anisyl-3-ezhyl-5-phenoxy-Z-thiazolel [2-(3-ethyl-4-keto-2 thi05 thiazolfidinylidene)-3- ethylS-thiazolidJ-one] dimethinemer acyanine S1 01B! otmo-o 0=CN 0=o-N-c,m

= O=CH-CH= =3 =5 This dye was obtained ascoppery crystals, M. P. 278'C., from pyridine methanol with sensitizing maxima at 680 mu (AgClBrarid AgIBr).

Example 37. [4-p-anisyl-3-ethyl-5-phen0xy-2-ihiaz0le] [2-(3 ethyl 4ket0-2-thio-5-oxazolidinylidene)-3- ethyl-5-thiaz0lid-4-one]dimethinemerocyanine This dye was obtained as dark green needles, M. P.296 C., from pyridine-methanol with sensitizing rnaxiina a at 650 mu(AgClBr) and 640 mu (AgIBr).

Example 38. [4-p-anisyl-3- ethyl-5-phenoscy-2-thiazole l[2-(3-ethyl-ket0-2-thio 5 thiazolidinylidene) 3-methyl-4-thiaz6lid-50nel dimethinemerocyanine This dye was obtained asdark green needles, M. P.

253" C., from pyridine-methanol with sensitizing maxima Example 39.[4-p-anisyl-3-etl1yl-5-phehwiy-Z-tlziazolel [2-(3-ethyl-4-keto-2-thio 5oxazolidinylidene) 3- methyl-4-thiazolid-5- ne] dimethinemerocyanineThis dye was obtained as dark green needles, M. P. 233 C., frompyridine-methanol with a sensitizing maximum at 660 mu (AgClBr).

"This dye was cibtained as dark gmennged les, MQP.

N \or N mum at 680 mu(AgClBf)'.

2,748,272 s 17 18 Example 45.--l3-ethyl-5-p-chlorophen0xy 4 p-chloro-This dye was obtained as brown needles, M. P. 298 C., phenyl-2-thiazole][2-(3 ethyl-4-ket0-2-thi0-thiaz0lifrom pyridine-methanol withsensitizing maxima at 670 dinylidene) 3-ethyl 5 thiazlid-4-one]dimethinemu (AgClBr) and 660 mu (AgIBr).

merocyanine Example 49.-[3-ethyl-4-phenyl 5 p tol'ylthio 2 thia- CI QO-C0=C-N O=CN-G H Zola] [2-(3-ethyl-4-kelo-2-thi0 5 thiaz0lidinylidene)- llC=CH CH=& =8 3-m ethyl-4-thiazolid 5 one] dimetlzineme rocyaninec=cH-cn=. This dye was obtained as a green powder, M. P. 246 C., CqHr ii N s from pyridine-methanol with a sensitizing maximum at i N 6 650 mu(AgClBr).

411B; Example 46.-[3 ethyl-5-p-chlor0phenoxy-4-pchlorophenyl-z-fhiazolel y 5 This dye was obtained as green needles, M.P. 224 C., z y yl 4 IhiaZ0lid-5-0fle] dimelh' from pyridine-methanol. Itwas sensitized a gelatino silyanine ver chlorobromide emulsion withmaxima at 630 and i i 690 mu and a gelatine silver bromiodide emulsionwith maxima at 630 and 690 mu.

C10 N s Example 50.[3-ethyl-4-fl-naphthyl 5 p tolylthio 2- A thiazole][2-(3 ethyl-4-keto-2-thio 5 thiazolidinyli- (1 dene)-3-ethyl-5-thiaz0lid4 one] dimethinemerocyanine This dye was obtained asdark green needles,M. P. 275 (3., from pyridine-methanol with sensitizing maxima S (lg-H at665 mu (AgClBr) and 670 mu (AgIBr).

Example 47 .-[3-ethyl-5 -p-br0mophenoxy 4 p bromocmQs-ophenyl-Z-thiazole] [2-(3-ethyl-4-keto-2-thio 5 thia- 5 izolidinylidene)-3-methyl-4-thiazolid 5 one] dimethinemerocyanine s aBr-QQ-O O=CS Q=CN CRHU 40 This dye was obtained as green needles, M. P.247' C., =S from pyridine-methanol with a sensitizing maximum at G 660mu(AgClBr). Br N S \N Ha L Example 51.--[3-ethyl-4-/3-naphthyl 5 ptolylthio-Z- 2 5 l i thitlzole] [2-(3 ethyl-4-ket0-2-thio 5thiaz0lidinyli- This dye was obtained as green threads, M. P. 286 C., idene)-3-methyl-4-thiazolid 5 one] dimethinemerofrom pyridine-methanolwith sensitizing maxirna at 670 cyanine mu (AgClBr and AgIBr).

Example 48.-[3-elhyl 4 phenyl-S-p-tolylthio 2 thiadene)-3-ethyl 5thiaz0lid-4-0ne] dimethinemerocy- C=CH-CH=J3 0:0 :3

anime S CzHa (I33 C=GHCH=(iZ =s This dye was obtained as a violetpowder, M. P. 296 C., from pyridine-methanol. It sensitized a gelatinesilver J} i chlorobromide emulsion with maxima at 630 and 680 X mu.

Example 52.-[4-p-anisyl-3-methyl 5 phen0xy-2-thiazole][5-(4-p-anisyl-3-methyl 5phenoxy-Z-thiazolidinylideneethylidene)-3-ethylthiaz0l-4 one]methz'necyanine-p-toluenesulphonate 20 Example 55.-[;?methyl-.i-phermxyr4rphenyl-2-thiazolel [4 1 (3 1 ethyl ,2benzothigzqlinylide ne ethylidene)-3- methyl-2-thia;l-5-one]methinecyanine iodine This dye was obtained as coppery threads,M. P. 242

Example 53.-[4-p-anisyl-3-ethyl 5 phenyl-Z-thiazole][5-(4-p-anisyl-3-methyl 5 p (t-OctyDphehOxy-Z-thiazolidinylideneethylidene)-3-ethyl 2 thiazol 4- one] methinecyanineiodide This dye was obtained as purple needles, M. P. 224 C., frompyridine-methanol with a sensitizing maximum at 650 m (AgClBr). IExample 54 [3 methyl-5-phenoxy-4-phenyl-2thiaz0le] [4-(3 ethyl 4,5 benzZ-benzothiazolinylideneethylidene) 3 methyl 2thiazol-S-onelmethinecyanine-p- S QaHs C., from pyridine-ether with asensitizing maxima at 660 (AgClBr and AgIBr).

Example 56.[3 methyl-5-phen0xy-4-phenyl-Z-thiazole] [4 7 (3 7 ethyl21benzoselenazoli ylideneethylidene)-3-methyl-Z-thiazol-fi-one]methinecyanine iodide 263 Cd'from pyridine witha sensitizing maximum at This dye was obtained as violet threads, M. P.264 C,, 670 mn.

Example 57.-[3 methyl 5-p-bromophenoxy-4-p-bromophenyl 2thiaz0le][4-(3-ethyl-5-p-bromophehoxy-4-pbromophenyl-2-thiazolinylideneethylidene)-3-methyl-2-thiazol-5-one]methinecyanine iodide This dye was obtained as greenflakes, M. P. 190 C., from methanol, with a sensitizing maximum at 670me.

from pyridine-methanol It sensitized a gelatino-silver xqmple58.T[3:methyl-4-phenyl-5-p-tolylthio-2-thiazole] [5 (3 ethyl4-phenyl-5-p-tolylthio-2-thiazolinylideneethylidene) 3 thyl 2thiazol-4-one]methinecyanine This dye was obtained as green needles, M.P. 233 C., from pyridine-ether, with sensitizing maxima at 660 my. .75.(AgClBr) and 670 mp (AgIBr).

chlorobromide emulsion with maxima at 630 and 690 m u and agelatino-silver bromiodide emulsion with maxima at 630 and 690 mp.

2,748,272 21 p p 22 Example59.-[3-methyl-4-phenyl-5-p-tolylthio-Z-thiazole] [4(3-methyl-4-phenyl-5-p-tolylthio-2-thiazolinylideneethylidene) 3methyl-24hiazol-5-onc]methinecyanine iodide This dye was obtained asviolet threads, M. P. 205 C., in the art upon making the ordinary testsand observafrom pyridine-ether, with sensitizing maxima at 630 m tionscustomarily used in the art of emulsion making. (AgClBr) and (AgIBr) and690 m (AgClBr and To prepare a gelatino-silver-halide. emulsionsensitized AgIBr). 1 with one of our new dyes, the following procedureis satis- Example 60.-[3 methyl 4 fi-naphthyl-S-p-tolylthi-2- thz'azole][5-(3-ethyl-4-B-naphthyl-5-p-tolylthio-2-thiaz0- linylideneethylidene) 3ethyl-2-thiazol-4-one]methinecyanine iodide This dye was obtained asviolet threads, M. P. 241 C., factory: A quantity of the dye isdissolved in methyl from pyridine-ether, with a sensitizing maximum at670 alcohol or other suitable solvent and a volume of this m (AgClBr).solution (which may be diluted with water) containing Example 61.[3-methyZ-4-B-mtphthyl-5-p-tolylthio-Z-thiazole] [4(S-methyl-4-,8-naphzjhyl-S-pfiolylthio-Z-thiazolinylideneethylidene-3-methyl-2-thiazol-S-oitelmethinecyanine iodide N i (in (iTHq a 61 13V\I This dye was obtained as a bronze-violet powder, M. P. from 5 to 100mgs. of dye is slowly added to about 1000 222 C., from pyridine-etherwith sensitizing maxima a cc. of a gelatino-silver-halide emulsion, withstirring. 630 my (AgCl and 670 u U- Stirring is continued until the dyeis uniformly distributed The y 0f EXamples 54, 55, and 56 Were Pmparedby K0 throughout the emulsion. With most of our .new dyes, l0 condensingthe quaternized merocyanine dyes of Aubert, to mgs. of dyfi per liter ofemulsion suffices to produce Jeifreys, and Knott US. application SerialNo. 220,332, filed March 2, 1951, U. S. Patent 2,656,351, issued Octoberthe maxlmum sansmzmg efiect Wlth the Drdmary gelat inc-silver bromide(including bromiodide) emulsions. y 215 225 1 yggi fgg g l gg fi i sg:With fine-grain emulsions, which include most of the ordi-' densationswere eifected in ethanol with triethylamine as 55 Barfly employedgelafimsilver-chloride emulsions some the condensing agent. This type ofprocess is described What larger concantranons of dye may be necessaryto in detail in Serial No. 220,332. The dyes thus produced Secure theoptlmum senslfizmg effect can be represented by the following generalformula: The above statements are only illustrative and are not Xvi. s

O=C S o-x-m uti-r en=on ...i b=on-on= s (i=oH-o g wherein R, R1, R2, R3,R4, X3, X, n, and Z each have the to be understood as limiting ourinvention in any sense, values given above. as it will be apparent thatour new dyes can be incorpo- The concentration of our new dyes in theemulsion rated by other methods in many of the photographic an varywidely, i, e from about 5 to about 100 mg silver halide emulsionscustomarily employed in the art. per liter of flowable emulsion. Theconcentration of the For instance, the dyes can be incorporated bybathing dye will vary according to the type of light-sensitive maa plateor film upon which an emulsion has been coated, terial in the emulsionand according to the effects dein the solution of the dye, in anappropriate solvent. sired. The suitable and most economicalconcentration Bathing methods, however, are not to be preferred for anygiven emulsion will be apparent to those skilled ordinarily.

23 What I claim as my invention and desired secured by Letters Patent ofthe United States is:

1. A polymethine dye selected from the group consisting of thoserepresented by the following general formulas: 5 4 aryl 5 arylthio 2thiazolinylidene ethylidene) R5 3-alkyl-2-thiazol-5-one]methinecyaninedye having the s RrX-O 7 i l following formula.

R C=OHOH=( J\ B=e been S a S R -s-o 0:0 S o-s a f o=oH-orr=d =OH-O/ 2 RR1- R1 N N r S l 4 O=O-1-S /Q\ R R3 X: B xo I 1" (UJ o=on-on= b=6--o=o 0B wherein R1 and R2 each represents an aryl group, R, R3 N a and R4 eachrepresents an alkyl group of from 1 to 2 i carbon atoms and X:represents an acid radical.

0 O N R m-x-o ,p

R g o=oH-oH=o\ /C=CHU(=CH--CH)n- =IiI-R l S X:

S O C--S m-x-o g R C==OH-CH=C =OH-C(==0H-CH)n-1=ITT-R wherein R, Rs, R4,and R5 each represents an alkyl group containing from 1 to 2 carbonatoms, R1 and R2 each represents a monocyclic aryl group of the benzeneseries, X represents a member selected from the group consisting of anoxygen atom and a sulfur atom, Q represents the non-metallic atomsnecessary to complete a heterocyclic nucleus containing 5 atoms in thehetero of those of the thiazole series, those of the benzothiazole yseries, those of the naphthothiazole series, those of theth'ianaphtheno-7,6',4,5-thiazole series, those of the oxazole series,those of the benzoxazole series, those of the naphthoxazole series,those of the selenazole series,

those of the benzoselenazole series, those of the naphthoselenazoleseries, those of the thiazoline series, those of the 2-quinoline series,those of the 4-quinoline series;

those of the l-isoquinoline series, those of the 3-isoquino line series,those of the 3,3-dialkylindolenine series, those of the Z-pyridineseries, and those of the 4-pyridine series.

2. A [3-alkyl-4-aryl-5-arylthio-2-thiazole] [5-(3-alky1- 4 aryl 5 -ary1t hio 2 thiazolinylidene ethylidene) 3 alkyl 2 thiazol 4onelrnethinecyanine dye having the following formula:

it V 113 \X herein R; nd 2 ash r pr e an a yl p, R, s

and R each represents an alkyl group of from 1 to 2 carbon atoms, and X3represents an acid radical.

3. A [3-alkyl-4-aryl-5-arylthi -Z-PhlaZOIe] [4(3-alkyl- 4. A[3-alkyl-5-ary1oxy-4-ary1-2-thiazole] [2-(3-a1kyl- 4 keto 2 thio 5thiazolidinylidene) 3 alkyl 5 thiazolid-4-one]dimethinemerocyanine dyehaving the following formula:

wherein R1 and R2 each represents an aryl group, and R, R4 and R5 eachrepresents an alkyl group of from 1 to 2 carbon atoms.

6. A t3-alkyl-5'-aryloxy-4-aryl-2 thiazole] [2-(3-a1kyl- 4 keto 2 thio 5oxazolidinylidene) 3 alkyl 4 H 2,748,272 25 26thiazolid-4-one]dimethinemerocyanine dye having the represents an acidradical, with a compound selected following formula: i from thoserepresented by the following general R i formulas: S v g IQ\ RPO C/ 0=CN N R| 6/ \b t R g C=CH-OH=$\ /=l\ =5 Ha =0 1 S o and f e J R i l0 N7:OHOH), U-OH wherein R1 and R2 each represents an aryl group, and X3 i iR, R4 and R5 each represents an alkyl group of from wherein Q representsthe non-metallic atoms necessary 1 to 2 carbon atoms. to complete aheterocyclic nucleus containing 5 atoms 7. A polymethine dye representedby the following in the heterocyclic ring, 3 of said atoms being carbonformula: atoms, 1 of said atoms being a nitrogen atom, and 1 of S0=C---\T-0 H on? s-o l 2 6 o-s om i! O=CH-0H= =OH-O 1L H B U S 8 6 N N\211s 0%; I V 8. A polymethine dye represented by the following saidatoms being selected from the group consisting of formula: an oxygenatom and a sulfur atom, R3 represents an CaHr-(J u s \N H X (5H9 3 CH3 I9. A polymethine dye represented by the following alkyl group, X;represents an acid radical, n represents formula: 21 positive integer offrom 1 to 2, and Z represents the 02H 0 non-metallic atoms necessary tocomplete a heterocyclic nucleus selected from the group consisting ofthose of 0:0 N N CYH5 the thiazole series, those of the benzothiazoleseries, those O=CHOH=(IJ 1: =8 of the naphthothiazole series, those ofthe thianaph cans theno7,6,4,5-thiazole series, those of the oxazoleseries, N those of the benzoxazole series, those of the naphthox- 4Oazole series, those of the selenazole series, those of the'benzoselenazole series, those of the naphthoselenazole A palymethinedye represented by the following series, those of the thiazoline series,those of the 2-quinoformula: line series, those of the 4-quinolineseries, those of the O H O S 0 l-isoquinoline series, those of the3isoquinoline series, i j, 5 those of the 3,3-dialkylindolenine series,those of the O C=GH$H=$ 1 6 0:5 2-pyridine series, and those of the4-pyridine series. Onto-Gi i 13. A process for preparing polymethinedyes com- N S prising condensing a compound selected from those rcp- A13, resented by the following general formula:

11. A polymethine dye represented by the following X C s 0=o--s Rformula. 2 c=0r 033=d d-s-m R1 \\I% CeH5O S I r 0-0 Noun b Nous, R1 CH OC=CH-OH= '=s R 3 \S/ 0 wherein R, R4 and Rs each represents an .alkylgroup N containing from 1 to 2 carbon atoms, R1 and R2 each dimrepresents a monocyclic aryl group of the benzene series,

0 X represents a member selected from the group consisting of any oxygenatom and a sulfur atom, and X4 represents an acid radical, with acompound selected from those represented ,by the following generalformulas:

12. A process for preparing polymethine dyes com prising condensing acompound selected from those represented by the following generalformula:

R'lfg C CH CH \S/ 3 RI H:6--b=0 N and It e .cr wherein R, R4 and R5 eachrepresents an alkyl group NZ: H, containing from 1 to 2 carbon atoms, R1and R2 each represents a monocyclic aryl group of the benzene series, Xrepresents a member selected fromthe group conwherein Q represents thenon-metall1c atoms necessary sisting of an oxygen atom and a sulfuratom, and X4 to complete a heterocyclic nucleus containing 5 atoms inthe heterocyelic ring, 3 of said atoms being car-hon atoms, 1 of saidvatoms being a nitrogen atom, and 1 of said atoms being selected fromthe group consisting of an oxygen atom and a sulfur atom, R3 representsan alkyl group, X3 represents an acid radical, n represents a positiveinteger of from 1 to 2, and Z represents the non-metallic atomsnecessary to complete a heterocyclic nucleus selected from the, groupconsisting of 7 those of the thiazole series, those of the benzothiazoleseries, those of the haphthothiazole series, those of thethianaphtheno-7,6',4,5-thjazole series, those of the oxazole series,those of the benzoxazole series, those of the naphthoxazole series,those ofthe selenazole series,

those of the benzoselenazole series, those of the naphthoselenazoleseries, those of the thiazoline series, those of the 2-quinoline series,those of the 4-quinoline series, those of the l-isoquinoline series,those of the 3-isoquinoline series, those of the 3,3-dialkylindolenineseries, those of the 2-pyridine series, and those of the 4-pyridineseries.

References Cited in the file of this patent UNITED STATES PATENTS

1. A POLYMETHINE DYE SELECTED FROM THE GROUP CONSISTING OF THOSEREPRESENTED BY THE FOLLOWING GENERAL FORMULAS: